Rapid prototyping resin compositions

• US 8,293,810 B2
• Filed: 08/29/2005
• Issued: 10/23/2012
• Est. Priority Date: 08/29/2005
• Status: Active Grant

• Current Assignee: CMET Inc. (Nabtesco Corporation), Shin-Etsu Chemical Company Limited
• Original Assignee: CMET Inc. (Nabtesco Corporation), Shin-Etsu Chemical Company Limited
• Inventors: Ito, Takashi, Ozai, Toshiyuki, Miyao, Takeshi, Hagiwara, Tsuneo
• Primary Examiner(s): PEPITONE, MICHAEL F
• Application Number:
  US11/212,711
• Publication Number:
  US 20070049652A1
• Time in Patent Office: 2,612 Days
• Field of Search: 522/99, 522/79, 522/148, 522/172, 522/8, 522/46, 106/287.13, 556/465, 528/22, 528/32, 528/33, 524/860
• US Class Current: 522/148
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Abstract

A resin composition suited for rapid prototyping is provided comprising (I) an actinic energy radiation-curable silicone composition, (II) an actinic energy radiation-sensitive polymerization initiator, and (III) an actinic energy radiation absorber. The resin composition experiences little viscosity buildup and maintains fluidity during long-term storage at elevated temperature, and is effective in rapid prototyping or shaping by stereolithography using any actinic energy radiation.

Claims

1. A resin composition for forming a three-dimensional object by a stereolithography technique comprising steps of selectively irradiating an ultraviolet laser beam to the surface of liquid photo-curable resin contained in a vat under the control of a computer to harden the photo-curable resin so that a photo-cured resin layer having a predetermined thickness is obtained, then supplying a layer of liquid photo-curable resin onto the cured resin layer and then likewise irradiating an ultraviolet laser beam to the liquid photo-curable resin layer to form a cured resin layer contiguous to the previous cured resin layer, and repeating said steps until a desired three-dimensional object is obtained,

said resin composition comprising:

(I) an actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber,

the actinic energy radiation-curable silicone composition (I) comprising

(A) an alkenyl-containing organopolysiloxane having the general formula (1);

2. The resin composition of claim 1 which upon exposure to actinic energy radiation, cures into a product which exhibits such elastomeric physical properties in a tensile test according to JIS K-7113 that a specimen having the same shape and size as a dumbbell for the tensile test according to JIS K-7113 has an elongation of at least 100% and has a percent elastic recovery L0/L1 of at least 80%, provided that L0 is a length before elongation and L1 is a length after elongation.

3. The resin composition of claim 1 which upon exposure to actinic energy radiation, cures into a product which exhibits such elastomeric physical properties in a tensile test that it maintains a percent elastic recovery of at least 80% after elongation of at least 100% for a duration of at least one month.

4. The resin composition of claim 1 wherein the amount of the actinic energy radiation absorber (III) is 0.001 to 0.25 part by weight per part by weight of the polymerization initiator (II).

5. The resin composition of claim 1, wherein the weight ratio of (A)/(B) is 85/15 to 95/5.

6. The resin composition of claim 1, wherein the amount of the actinic energy radiation absorber (III) is 0.025 to 0.25 parts by weight per part by weight of the polymerization initiator (II).

7. The resin composition of claim 1, wherein the amount of the actinic energy radiation-sensitive polymerization initiator (II) is 0.5 to 5 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I),

the amount of the actinic energy radiation absorber (III) is 0.01 to 0.25 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I), and

the amount of the actinic energy radiation absorber (III) is 0.025 to 1 part by weight per 100 parts by weight of the polymerization initiator (II).

8. The resin composition of claim 1, wherein R¹ is methyl or phenyl.

9. A method of forming a three-dimensional object by a stereolithography technique comprising

irradiating actinic energy radiation to the surface of a liquid resin composition comprising

(I) an actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber,

so as to form a cured resin layer having a predetermined pattern, then supplying an uncured layer of the liquid resin composition onto the cured resin layer, then irradiating actinic energy radiation to the liquid resin composition to form a cured resin layer contiguous to the previous cured resin layer, and repeating the laminating steps until a desired three-dimensional object is obtained,

said resin composition comprising:

(I) all actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber,

the actinic energy radiation-curable silicone composition (I) comprising

(A) an alkenyl-containing organopolysiloxane having the general formula (1);

10. The method of claim 9 wherein the resin composition, upon exposure to actinic energy radiation, cures into a product which exhibits such elastomeric physical properties in a tensile test according to JIS K-7113 that a specimen having the same shape and size as a dumbbell for the tensile test according to JIS K-7113 has an elongation of at least 100%, resumes the original shape after the tensile stress is relieved, and has a percent elastic recovery L0/L1 of at least 80%, provided that L0 is a length before elongation and L1 is a length after elongation.

11. The method of claim 9 wherein the resin composition, upon exposure to actinic energy radiation, cures into a product which exhibits such elastomeric physical properties in a tensile test that it maintains a percent elastic recovery at a least 80% after elongation of at least 100% for a duration of at least one month.

12. The method of claim 9 wherein the amount of the actinic energy radiation absorber (III) is 0.001 to 0.25 part by weight per part by weight of the polymerization initiator (II).

13. The method of claim 9, wherein the weight ratio of (A)/(B) is 85/15 to 95/5.

14. The method of claim 9, wherein the amount of the actinic energy radiation absorber (III) is 0.025 to 0.25 parts by weight per part by weight of the polymerization initiator (II).

15. The method of claim 9, wherein the amount of the actinic energy radiation-sensitive polymerization initiator (II) is 0.5 to 5 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I),

the amount of the actinic energy radiation absorber (III) is 0.01 to 0.25 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I), and

the amount of the actinic energy radiation absorber (III) is 0.025 to 1 part by weight per 100 parts by weight of the polymerization initiator (II).

16. The method of claim 9, wherein R¹ is methyl or phenyl.

17. A resin composition for forming a three dimensional object by a stereolithography technique comprising steps of selectively irradiating an ultraviolet laser beam to the surface of liquid photo-curable resin contained in a vat under the control of a computer to harden the photo-curable resin so that a photo-cured resin layer having a predetermined thickness is obtained, then supplying a layer of liquid photo-curable resin onto the cured resin layer and then likewise irradiating an ultraviolet laser beam to the liquid photo-curable resin layer to form a cured resin layer contiguous to the previous cured resin layer, and repeating said steps until a desired three-dimensional object is obtained,

said resin composition comprising:

(I) an actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber;

the actinic energy radiation-curable silicone composition (I) comprising

(A) an alkenyl-containing organopolysiloxane having the general formula (1);

18. The resin composition of claim 17 wherein the amount of the actinic energy radiation absorber (III) is 0.001 to 0.25 part by weight per part by weight of the polymerization initiator (II).

19. The resin composition of claim 17, wherein the amount of the actinic energy radiation absorber (III) is 0.025 to 0.25 parts by weight per part by weight of the polymerization initiator (II).

20. The resin composition of claim 17, wherein the amount of the actinic energy radiation-sensitive polymerization initiator (II) is 0.5 to 5 parts by weight per 100 parts by weight of the actinic energy radiation-curable, silicone composition (I),

the amount of the actinic energy radiation absorber (III) is 0.01 to 0.25 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I), and

the amount of the actinic energy radiation absorber (III) is 0.025 to 1 part by weight per 100 parts by weight of the polymerization initiator (II).

21. A method of forming a three-dimensional object by a stereolithography technique comprising

irradiating actinic energy radiation to the surface of a liquid resin composition comprising

(I) an actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber,

so as to farm a cured resin layer having a predetermined pattern, then supplying an uncured layer of the liquid resin composition onto the cured resin layer, then irradiating actinic energy radiation to the liquid resin composition to farm a cured resin layer contiguous to the previous cured resin layer, and repeating the laminating steps until a desired three-dimensional object is obtained,

said resin composition comprising:

(I) an actinic energy radiation-curable silicone composition,

(II) an actinic energy radiation-sensitive polymerization initiator, and

(III) an actinic energy radiation absorber,

the actinic energy radiation-curable silicone composition (I) comprising

(A) an alkenyl-containing organopolysiloxane having the general formula (1);

22. The method of claim 21, wherein the amount of the actinic energy radiation absorber (III) is 0.001 to 0.25 part by weight per part by weight of the polymerization initiator (II).

23. The method of claim 21, wherein the amount of the actinic energy radiation absorber (III) is 0.025 to 0.25 parts by weight per part by weight of the polymerization initiator (II).

24. The method of claim 21, wherein the amount of the actinic energy radiation-sensitive polymerization initiator (II) is 0.5 to 5 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I),

the amount of the actinic energy radiation absorber (III) is 0.01 to 0.25 parts by weight per 100 parts by weight of the actinic energy radiation-curable silicone composition (I), and

the amount of the actinic energy radiation absorber (III) is 0.025 to 1 part by weight per 100 parts by weight of the polymerization initiator (II).